CN116253852B - Preparation method of modified thermoplastic polyurethane elastomer - Google Patents
Preparation method of modified thermoplastic polyurethane elastomer Download PDFInfo
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- CN116253852B CN116253852B CN202211653050.0A CN202211653050A CN116253852B CN 116253852 B CN116253852 B CN 116253852B CN 202211653050 A CN202211653050 A CN 202211653050A CN 116253852 B CN116253852 B CN 116253852B
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- zinc oxide
- thermoplastic polyurethane
- rare earth
- polyurethane elastomer
- diisocyanate
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 44
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 43
- 239000000806 elastomer Substances 0.000 title claims abstract description 43
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002077 nanosphere Substances 0.000 claims abstract description 58
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 54
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 48
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 40
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 32
- 150000002009 diols Chemical class 0.000 claims abstract description 31
- 229920000728 polyester Polymers 0.000 claims abstract description 31
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 28
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 28
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 28
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 28
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 25
- 239000011787 zinc oxide Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 81
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 30
- 239000004246 zinc acetate Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 28
- 238000002791 soaking Methods 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 16
- -1 rare earth acetate Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 230000000630 rising effect Effects 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 4
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- FOGKDYADEBOSPL-UHFFFAOYSA-M rubidium(1+);acetate Chemical compound [Rb+].CC([O-])=O FOGKDYADEBOSPL-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000005470 impregnation Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 37
- 229910052799 carbon Inorganic materials 0.000 abstract description 37
- 229920002635 polyurethane Polymers 0.000 description 12
- 239000004814 polyurethane Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229920003225 polyurethane elastomer Polymers 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a preparation method of a modified thermoplastic polyurethane elastomer, which comprises the following steps: s1, adding rare earth doped porous zinc oxide micro-nanospheres into microcrystalline cellulose solution, then adding citric acid, uniformly dispersing, and reacting at high temperature to obtain carbon sphere modified zinc oxide porous micro-nanospheres; s2, heating the polyester diol and the carbon sphere modified zinc oxide porous micro-nano spheres prepared in the step S1, dehydrating in vacuum, and then mixing and stirring to obtain a mixture A; s3, mixing diisocyanate and 1, 4-butanediol, then adding the mixture A prepared in the step S2, stirring and curing to obtain the modified thermoplastic polyurethane elastomer. According to the invention, the carbon sphere modified zinc oxide porous micro-nanospheres are added, so that the heat resistance and mechanical properties of the thermoplastic polyurethane elastomer are improved.
Description
Technical Field
The invention relates to the field of preparation of high polymer materials, in particular to a preparation method of a modified thermoplastic polyurethane elastomer.
Background
The [0002 ] polyurethane elastomers can now be divided into three categories: cast polyurethane elastomers, compounded polyurethane elastomers, and thermoplastic polyurethane elastomers. The thermoplastic polyurethane elastomer is a linear or slightly branched or crosslinked polymer material prepared from oligomer dihydric alcohol containing active hydrogen, an organic diisocyanate compound and a small molecular diol (or diamine) chain extender through gradual addition polymerization reaction. The thermoplastic polyurethane elastomer has both plastic processing performance and physical and mechanical properties and strength performance of rubber, and has excellent wear resistance, oil resistance, low temperature resistance and radiation resistance. Thermoplastic polyurethane elastomers can be made into various industrial articles by extrusion, injection, film blowing, calendaring, spinning, etc., and their application is almost penetrating into various industrial fields.
The thermoplastic polyurethane elastomer has the advantages of high mechanical strength, good wear resistance and toughness, excellent oil resistance, shock absorption and radiation resistance, good processability, wide application range and the like, and the application range is wider and wider. However, thermoplastic polyurethane elastomers have low softening and decomposition temperatures, relatively poor heat resistance, and also have large internal heat generation, and require attention to release heat during use, which limits their range of applications. The thermoplastic polyurethane elastomer is usually used at a temperature of not higher than 80 ℃ and can be used for a short period at 120 ℃, and if it is acted for a long time under high-frequency oscillation or high-temperature conditions, the mechanical properties are reduced or the functions are lost. The thermal decomposition temperature of polyurethane is not high, so that the polyurethane is greatly limited in use at higher temperature. Accordingly, corresponding modifications must be made in the formulation or structural design to enhance the heat resistance. Fillers such as calcium carbonate, carbon black, quartz stone, carbon fiber, glass fiber, nylon, cured resin particles and the like are often used in the synthesis of polyurethane elastomers, and can improve the thermal stability of polyurethane. In addition, the heat resistance of polyurethane can be improved by adding some heat-resistant materials such as glass fiber, molecular sieve and the like into polyurethane through a physical method. The heat resistance of the polyurethane is improved, the application range of the polyurethane can be expanded, the service life of the thermoplastic polyurethane elastomer can be prolonged, the maintenance and repair cost caused by ageing of the polyurethane is reduced, and the environmental pollution caused by waste of materials is reduced.
Disclosure of Invention
The technical problems to be solved are as follows: the invention aims to provide a preparation method of a modified thermoplastic polyurethane elastomer, which improves the heat resistance and mechanical property of the thermoplastic polyurethane elastomer by adding carbon sphere modified zinc oxide porous micro-nano spheres.
The technical scheme is as follows: a method for preparing a modified thermoplastic polyurethane elastomer, comprising the following steps:
S1, adding rare earth doped porous zinc oxide micro-nanospheres into microcrystalline cellulose solution, then adding citric acid, uniformly dispersing, and reacting at high temperature to obtain carbon sphere modified zinc oxide porous micro-nanospheres;
s2, heating the polyester diol and the carbon sphere modified zinc oxide porous micro-nano spheres prepared in the step S1, dehydrating in vacuum, and then mixing and stirring to obtain a mixture A;
S3, mixing diisocyanate and 1, 4-butanediol, then adding the mixture A prepared in the step S2, stirring and curing to obtain the modified thermoplastic polyurethane elastomer.
Preferably, in the step S1, the mass ratio of the rare earth doped porous zinc oxide micro-nanospheres to the microcrystalline cellulose is 10:1-2:1-5, and the concentration of the microcrystalline cellulose solution is 2-5g/L.
Preferably, the high temperature reaction in the step S1 is carried out at 160-220 ℃ for 10-20 hours.
Preferably, the rare earth doped porous micro-nano spheres in the step S1 are prepared by the following steps:
s11, preparing a rare earth acetate solution and a zinc acetate solution respectively;
S12, adding the dried pollen into a mixed solution of a rare earth acetate solution and a zinc acetate solution, carrying out ultrasonic dispersion treatment on the solution, and filtering the pollen by adopting a suction filtration mode after soaking to obtain a pollen material with surface coating treatment; or soaking the dried pollen in zinc acetate solution, dispersing with ultrasonic wave, centrifuging after soaking for a period of time, soaking and suction filtering the filtered material with rare earth acetate solution to obtain pollen material with surface coating treatment;
and S13, calcining the pollen material prepared in the step S12 at high temperature to obtain the rare earth doped porous micro-nano spheres.
Preferably, the rare earth acetate solution in the step S11 comprises lanthanum acetate, cerium acetate and rubidium acetate, the concentration of the rare earth acetate solution is 2-5wt% and the concentration of zinc acetate is 6-14wt%.
Preferably, in the step S12, the volume ratio of the rare earth acetate solution to the zinc acetate solution is 1:1, the mass fraction of pollen in the solution is 3-6wt%, the ultrasonic dispersion time is 2-4h, and the soaking time is 20-40h.
Preferably, the temperature rising rate of the calcination in the step S13 is 1.5-2.5 ℃/min, the temperature is finally raised to 600-660 ℃, and the heat preservation time is 60-120min.
Preferably, in the step S2, the mass ratio of the polyester diol, the diisocyanate and the 1, 4-butanediol is 90-100:40-55:10-20, wherein the molecular weight of the polyester diol is 2000-2500g/mol, and the diisocyanate is any one of toluene diisocyanate, 4-diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, isophorone diisocyanate or 1, 4-cyclohexane diisocyanate.
Preferably, the curing time in the step S3 is 4-6 hours.
Preferably, the mass percentage of the carbon sphere modified zinc oxide porous micro-nano is 0.5-2.5wt%.
The beneficial effects are that: the preparation method of the modified thermoplastic polyurethane elastomer has the following advantages:
1. According to the invention, zinc oxide is a heat-resistant and heat-insulating material, but the surface of zinc oxide has no active group, so that carbon spheres are generated by modification on the surface and the inside of zinc oxide through a hydrothermal method, the surface of the prepared carbon sphere modified zinc oxide porous micro-nano spheres contains hydroxyl groups, the hydroxyl groups can react with diisocyanate, namely the prepared polyurethane system contains the carbon sphere modified zinc oxide porous micro-nano spheres, both the carbon spheres and the zinc oxide have higher heat resistance, and the carbon sphere modified zinc oxide porous micro-nano spheres can absorb heat, so that the penetration of heat into polymers is reduced, and the heat resistance of the material is improved;
2. Besides, when the carbon sphere modified zinc oxide porous micro-nano sphere is synthesized, rare earth elements are added, and the addition of the rare earth elements can obviously prevent the movement of molecules in the heating process and improve the heat resistance of the material;
3. In the invention, zinc oxide is prepared into a porous form, one is to facilitate the attachment of carbon spheres, and the porous structure can enable the molecular weight to be mutually inserted and filled in the polyurethane generation process to form a meshed structure, so that the binding force of the carbon sphere modified zinc oxide porous micro-nano spheres and polyurethane is improved, and the mechanical property is ensured not to be influenced by filler.
Detailed Description
The invention is further described below with reference to the following examples, which are illustrative of the invention and are not intended to limit the invention thereto:
example 1
A method for preparing a modified thermoplastic polyurethane elastomer, comprising the following steps:
S1, adding rare earth doped porous zinc oxide micro-nanospheres into microcrystalline cellulose solution, then adding citric acid, wherein the mass ratio of the microcrystalline cellulose to the citric acid is 10:1:1, the concentration of the microcrystalline cellulose solution is 5g/L, after uniform dispersion, carrying out high-temperature reaction at 220 ℃ for 10 hours, and obtaining carbon sphere modified zinc oxide porous micro-nanospheres, wherein the rare earth doped porous micro-nanospheres are prepared by the following steps:
s11, preparing a lanthanum acetate solution and a zinc acetate solution respectively, wherein the concentration of the lanthanum acetate solution is 5wt% and the concentration of the zinc acetate is 14wt%;
s12, adding dried pollen into a mixed solution of a lanthanum acetate solution and a zinc acetate solution, wherein the mass fraction of the pollen in the solution is 3wt%, the volume ratio of the lanthanum acetate solution to the zinc acetate solution is 1:1, carrying out ultrasonic dispersion treatment on the solution for 4 hours, soaking for 40 hours, and filtering the pollen by adopting a suction filtration mode to obtain a pollen material with a surface coated;
S13, calcining the pollen material prepared in the step S12 at a high temperature, wherein the temperature rising rate of calcination is 2.5 ℃/min, and finally, the temperature rises to 600 ℃, and the heat preservation time is 120min, so that the rare earth doped porous micro-nano spheres are obtained;
s2, heating the polyester diol and the carbon sphere modified zinc oxide porous micro-nano spheres prepared in the step S1, dehydrating in vacuum, and then mixing and stirring to obtain a mixture A;
s3, mixing diisocyanate and 1, 4-butanediol, then adding the mixture A prepared in the step S2, stirring and curing for 4 hours to obtain a modified thermoplastic polyurethane elastomer, wherein the mass ratio of the polyester diol to the diisocyanate to the 1, 4-butanediol is 90:40:10, wherein the molecular weight of the polyester diol is 2000g/mol, the diisocyanate is 4, 4-diphenylmethane diisocyanate, and the mass percentage of the carbon sphere modified zinc oxide porous micro-nano is 2.5wt%.
Example 2
A method for preparing a modified thermoplastic polyurethane elastomer, comprising the following steps:
S1, adding rare earth doped porous zinc oxide micro-nanospheres into microcrystalline cellulose solution, then adding citric acid, wherein the mass ratio of the microcrystalline cellulose to the citric acid is 10:2:5, the concentration of the microcrystalline cellulose solution is 2g/L, after uniform dispersion, carrying out high-temperature reaction at 160 ℃ for 20 hours, and obtaining carbon sphere modified zinc oxide porous micro-nanospheres, wherein the rare earth doped porous micro-nanospheres are prepared by the following steps:
S11, preparing a lanthanum acetate solution and a zinc acetate solution respectively, wherein the concentration of the lanthanum acetate solution is 2wt% and the concentration of the zinc acetate is 6wt%;
S12, adding dried pollen into a mixed solution of a lanthanum acetate solution and a zinc acetate solution, wherein the mass fraction of the pollen in the solution is 6wt%, the volume ratio of the lanthanum acetate solution to the zinc acetate solution is 1:1, carrying out ultrasonic dispersion treatment on the solution for 4 hours, soaking for 20 hours, and filtering the pollen by adopting a suction filtration mode to obtain a pollen material with a surface coated;
s13, calcining the pollen material prepared in the step S12 at a high temperature, wherein the temperature rising rate of calcination is 1.5 ℃/min, and finally, the temperature rises to 660 ℃, and the heat preservation time is 60min, so that the rare earth doped porous micro-nano spheres are obtained;
s2, heating the polyester diol and the carbon sphere modified zinc oxide porous micro-nano spheres prepared in the step S1, dehydrating in vacuum, and then mixing and stirring to obtain a mixture A;
s3, mixing diisocyanate and 1, 4-butanediol, then adding the mixture A prepared in the step S2, stirring and curing for 6 hours to obtain the modified thermoplastic polyurethane elastomer, wherein the mass ratio of the polyester diol, the diisocyanate and the 1, 4-butanediol is 9100:55:20, wherein the molecular weight of the polyester diol is 2500g/mol, the diisocyanate is 4, 4-diphenylmethane diisocyanate, and the mass percentage of the carbon sphere modified zinc oxide porous micro-nano is 0.5wt%.
Example 3
A method for preparing a modified thermoplastic polyurethane elastomer, comprising the following steps:
S1, adding rare earth doped porous zinc oxide micro-nanospheres into microcrystalline cellulose solution, then adding citric acid, wherein the mass ratio of the microcrystalline cellulose to the citric acid is 10:1.2:3, the concentration of the microcrystalline cellulose solution is 4g/L, after uniform dispersion, carrying out high-temperature reaction at 200 ℃ for 10 hours, and obtaining carbon sphere modified zinc oxide porous micro-nanospheres, wherein the rare earth doped porous micro-nanospheres are prepared by the following steps:
S11, preparing a cerium acetate solution and a zinc acetate solution respectively, wherein the concentration of the cerium acetate solution is 4wt% and the concentration of the zinc acetate is 12wt%;
s12, soaking dried pollen in zinc acetate solution, wherein the mass fraction of pollen in the solution is 4wt%, carrying out ultrasonic dispersion treatment for 2 hours, carrying out centrifugal filtration after the soaking time is 340 hours, soaking the filtered material in cerium acetate solution for 4 hours, and carrying out suction filtration to obtain a pollen material with surface coating treatment;
S13, calcining the pollen material prepared in the step S12 at a high temperature, wherein the temperature rising rate of calcination is 1.5 ℃/min, and finally, the temperature rises to 660 ℃, and the heat preservation time is 90min, so that the rare earth doped porous micro-nano spheres are obtained;
s2, heating the polyester diol and the carbon sphere modified zinc oxide porous micro-nano spheres prepared in the step S1, dehydrating in vacuum, and then mixing and stirring to obtain a mixture A;
S3, mixing diisocyanate and 1, 4-butanediol, then adding the mixture A prepared in the step S2, stirring and curing for 6 hours to obtain the modified thermoplastic polyurethane elastomer, wherein the mass ratio of the polyester diol to the diisocyanate to the 1, 4-butanediol is 90:45:12-20, wherein the molecular weight of the polyester diol is 2400g/mol, the diisocyanate is toluene diisocyanate, and the mass percentage of the carbon sphere modified zinc oxide porous micro-nano is 1wt%.
Example 4
A method for preparing a modified thermoplastic polyurethane elastomer, comprising the following steps:
s1, adding rare earth doped porous zinc oxide micro-nanospheres into microcrystalline cellulose solution, then adding citric acid, wherein the mass ratio of the microcrystalline cellulose to the citric acid is 10:1.6:4, the concentration of the microcrystalline cellulose solution is 3g/L, after uniform dispersion, carrying out high-temperature reaction at 180 ℃ for 20 hours, and obtaining carbon sphere modified zinc oxide porous micro-nanospheres, wherein the rare earth doped porous micro-nanospheres are prepared by the following steps:
s11, respectively preparing a cerium acetate solution and a zinc acetate solution, wherein the concentration of the cerium acetate solution is 3wt% and the concentration of the zinc acetate is 12wt%;
s12, firstly soaking dried pollen in zinc acetate solution, wherein the mass fraction of the pollen in the solution is 5wt%, carrying out ultrasonic dispersion treatment for 4 hours, carrying out centrifugal filtration after soaking for 30 hours, soaking the filtered material in cerium acetate solution for 2 hours, and carrying out suction filtration to obtain a pollen material with surface coating treatment;
S13, calcining the pollen material prepared in the step S12 at a high temperature, wherein the temperature rising rate of calcination is 2 ℃/min, and finally, the temperature rises to 600 ℃, and the heat preservation time is 110min, so that the rare earth doped porous micro-nano spheres are obtained;
s2, heating the polyester diol and the carbon sphere modified zinc oxide porous micro-nano spheres prepared in the step S1, dehydrating in vacuum, and then mixing and stirring to obtain a mixture A;
S3, mixing diisocyanate and 1, 4-butanediol, then adding the mixture A prepared in the step S2, stirring and curing for 6 hours to obtain the modified thermoplastic polyurethane elastomer, wherein the mass ratio of the polyester diol to the diisocyanate to the 1, 4-butanediol is 100:50:18, wherein the molecular weight of the polyester diol is 2200g/mol, the diisocyanate is toluene diisocyanate, and the mass percentage of the carbon sphere modified zinc oxide porous micro-nano is 2wt%.
Example 5
A method for preparing a modified thermoplastic polyurethane elastomer, comprising the following steps:
S1, adding rare earth doped porous zinc oxide micro-nanospheres into microcrystalline cellulose solution, then adding citric acid, wherein the mass ratio of the microcrystalline cellulose to the citric acid is 10:1.4:3.3, the concentration of the microcrystalline cellulose solution is 3.5g/L, after uniform dispersion, carrying out high-temperature reaction at 200 ℃ for 18 hours, and obtaining carbon sphere modified zinc oxide porous micro-nanospheres, wherein the rare earth doped porous micro-nanospheres are prepared by the following steps:
s11, preparing a cerium acetate solution and a zinc acetate solution respectively, wherein the concentration of the cerium acetate solution is 3.5wt% and the concentration of the zinc acetate is 10wt%;
S12, soaking dried pollen in zinc acetate solution, wherein the mass fraction of pollen in the solution is 4.5wt%, carrying out ultrasonic dispersion treatment for 3 hours, carrying out centrifugal filtration after the soaking time is 33 hours, soaking the filtered material in cerium acetate solution for 3 hours, and carrying out suction filtration to obtain a pollen material with surface coating treatment;
S13, calcining the pollen material prepared in the step S12 at a high temperature, wherein the temperature rising rate of calcination is 1.5 ℃/min, and finally, the temperature rises to 650 ℃, and the heat preservation time is 100min, so that the rare earth doped porous micro-nano spheres are obtained;
s2, heating the polyester diol and the carbon sphere modified zinc oxide porous micro-nano spheres prepared in the step S1, dehydrating in vacuum, and then mixing and stirring to obtain a mixture A;
S3, mixing diisocyanate and 1, 4-butanediol, then adding the mixture A prepared in the step S2, stirring and curing for 5 hours to obtain a modified thermoplastic polyurethane elastomer, wherein the mass ratio of the polyester diol, the diisocyanate and the 1, 4-butanediol is 95:45:14, wherein the molecular weight of the polyester diol is 2200g/mol, the diisocyanate is toluene diisocyanate, and the mass percentage of the carbon sphere modified zinc oxide porous micro-nano is 1.5wt%.
Comparative example 1
A method for preparing a modified thermoplastic polyurethane elastomer, comprising the following steps:
S1, adding zinc oxide micro-nanospheres into a microcrystalline cellulose solution, then adding citric acid and rare earth doped porous zinc oxide micro-nanospheres, wherein the mass ratio of microcrystalline cellulose to citric acid is 10:1.4:3.3, the concentration of the microcrystalline cellulose solution is 3.5g/L, and after uniform dispersion, carrying out high-temperature reaction at 200 ℃ for 18 hours to obtain carbon sphere modified zinc oxide micro-nanospheres;
s2, heating and vacuum dehydrating the polyester diol and the carbon sphere modified zinc oxide micro-nano spheres prepared in the step S1, and then mixing and stirring to obtain a mixture A;
S3, mixing diisocyanate and 1, 4-butanediol, then adding the mixture A prepared in the step S2, stirring and curing for 5 hours to obtain a modified thermoplastic polyurethane elastomer, wherein the mass ratio of the polyester diol, the diisocyanate and the 1, 4-butanediol is 95:45:14, wherein the molecular weight of the polyester diol is 2200g/mol, the diisocyanate is toluene diisocyanate, and the mass percentage of the carbon sphere modified zinc oxide porous micro-nano is 1.5wt%.
Comparative example 2
A method for preparing a modified thermoplastic polyurethane elastomer, comprising the following steps:
s1, adding porous zinc oxide micro-nanospheres into microcrystalline cellulose solution, then adding citric acid and porous zinc oxide micro-nanospheres, wherein the mass ratio of microcrystalline cellulose to citric acid is 10:1.6:4, the concentration of the microcrystalline cellulose solution is 3g/L, after uniform dispersion, carrying out high-temperature reaction at 180 ℃ for 20 hours, and obtaining carbon sphere modified zinc oxide porous micro-nanospheres, wherein the porous micro-nanospheres are prepared by the following steps:
S11, preparing zinc acetate solution, wherein the concentration of zinc acetate is 12wt%;
S12, soaking the dried pollen in zinc acetate solution, wherein the mass fraction of the pollen in the solution is 5wt%, carrying out ultrasonic dispersion treatment for 4 hours, and carrying out centrifugal filtration after soaking for 30 hours to obtain a pollen material with surface coating treatment;
S13, calcining the pollen material prepared in the step S12 at a high temperature, wherein the temperature rising rate of calcination is 2 ℃/min, and finally, the temperature rises to 600 ℃, and the heat preservation time is 110min, so that the porous micro-nano spheres are obtained;
s2, heating the polyester diol and the carbon sphere modified zinc oxide porous micro-nano spheres prepared in the step S1, dehydrating in vacuum, and then mixing and stirring to obtain a mixture A;
S3, mixing diisocyanate and 1, 4-butanediol, then adding the mixture A prepared in the step S2, stirring and curing for 6 hours to obtain the modified thermoplastic polyurethane elastomer, wherein the mass ratio of the polyester diol to the diisocyanate to the 1, 4-butanediol is 100:50:18, wherein the molecular weight of the polyester diol is 2200g/mol, the diisocyanate is toluene diisocyanate, and the mass percentage of the carbon sphere modified zinc oxide porous micro-nano is 2wt%.
Comparative example 3
A method for preparing a modified thermoplastic polyurethane elastomer, comprising the following steps:
S1, heating polyester dihydric alcohol and nano zinc oxide, dehydrating in vacuum, and then mixing and stirring to obtain a mixture A;
S2, mixing diisocyanate and 1, 4-butanediol, then adding the mixture A prepared in the step S2, stirring and curing for 6 hours to obtain a modified thermoplastic polyurethane elastomer, wherein the mass ratio of the polyester diol to the diisocyanate to the 1, 4-butanediol is 100:50:18, wherein the molecular weight of the polyester diol is 2200g/mol, the diisocyanate is toluene diisocyanate, and the mass percentage of the zinc oxide is 2wt%.
The polyurethane materials prepared in examples 1-5 and comparative examples 1-3 were subjected to comparative analysis of properties, and according to GB/T528-2009, mechanical properties were tested using a universal tester at a tensile rate of 100mm/min; the thermal decomposition temperature was measured by a thermogravimetric analyzer, and the specific test results are shown in the following table.
| Thermal decomposition temperature (. Degree. C.) | Tensile Strength (MPa) | Elongation at break (%) | |
| Example 1 | 252.3 | 45.9 | 426.8 |
| Example 2 | 248.6 | 49.3 | 440.3 |
| Example 3 | 250.7 | 46.8 | 432.5 |
| Example 4 | 251.3 | 46.2 | 433.9 |
| Example 5 | 252.4 | 47.4 | 439.5 |
| Comparative example 1 | 228.1 | 42.5 | 406.8 |
| Comparative example 2 | 231.3 | 43.1 | 409.2 |
| Comparative example 3 | 227.6 | 38.9 | 398.8 |
From the table, the carbon sphere modification and the rare earth element are added, so that the heat resistance of the material can be obviously improved, and the porous structure of zinc oxide has positive influence on the heat resistance and mechanical property.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (7)
1. The preparation method of the modified thermoplastic polyurethane elastomer is characterized by comprising the following steps of:
S1, adding rare earth doped porous zinc oxide micro-nanospheres into microcrystalline cellulose solution, then adding citric acid, uniformly dispersing, and then carrying out high-temperature reaction at 160-220 ℃ for 10-20 hours to obtain modified zinc oxide porous micro-nanospheres;
s2, heating the polyester diol and the modified zinc oxide porous micro-nano spheres prepared in the step S1, dehydrating in vacuum, and then mixing and stirring to obtain a mixture A;
S3, mixing diisocyanate and 1, 4-butanediol, then adding the mixture A prepared in the step S2, stirring and curing to obtain a modified thermoplastic polyurethane elastomer;
The rare earth doped porous zinc oxide micro-nano spheres in the step S1 are prepared by the following steps:
s11, preparing a rare earth acetate solution and a zinc acetate solution respectively;
S12, adding the dried pollen into a mixed solution of a rare earth acetate solution and a zinc acetate solution, carrying out ultrasonic dispersion treatment on the solution, and filtering the pollen by adopting a suction filtration mode after soaking to obtain a pollen material with surface coating treatment; or soaking the dried pollen in zinc acetate solution, dispersing with ultrasonic wave, centrifuging after soaking for a period of time, soaking and suction filtering the filtered material with rare earth acetate solution to obtain pollen material with surface coating treatment;
And S13, calcining the pollen material prepared in the step S12 at a high temperature, wherein the calcining temperature rising rate is 1.5-2.5 ℃/min, and finally, the temperature is raised to 600-660 ℃ and the heat preservation time is 60-120min, so that the rare earth doped porous zinc oxide micro-nano spheres are obtained.
2. The method for producing a modified thermoplastic polyurethane elastomer according to claim 1, wherein: in the step S1, the rare earth doped porous zinc oxide micro-nanospheres have the mass ratio of microcrystalline cellulose to citric acid of 10:1-2:1-5, and the concentration of the microcrystalline cellulose solution is 2-5g/L.
3. The method for preparing a modified thermoplastic polyurethane elastomer according to claim 1, wherein the rare earth acetate solution in the step S11 comprises lanthanum acetate, cerium acetate and rubidium acetate, the concentration of the rare earth acetate solution is 2-5wt%, and the concentration of the zinc acetate is 6-14wt%.
4. The method for preparing the modified thermoplastic polyurethane elastomer according to claim 1, wherein in the step S12, the volume ratio of the rare earth acetate solution to the zinc acetate solution is 1:1, the mass fraction of pollen in the solution is 3-6wt%, the ultrasonic dispersion time is 2-4h, and the impregnation time is 20-40h.
5. The method for producing a modified thermoplastic polyurethane elastomer according to claim 1, wherein the mass ratio of the polyester diol, the diisocyanate and the 1, 4-butanediol in the step S2 is 90 to 100:40-55:10-20, wherein the molecular weight of the polyester diol is 2000-2500g/mol, and the diisocyanate is any one of toluene diisocyanate, 4' -diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, isophorone diisocyanate or 1, 4-cyclohexane diisocyanate.
6. The method for producing a modified thermoplastic polyurethane elastomer according to claim 1, wherein the aging time in the step S3 is 4 to 6 hours.
7. The method for producing a modified thermoplastic polyurethane elastomer according to claim 1, wherein: the mass percentage of the modified zinc oxide porous micro-nanospheres is 0.5-2.5wt%.
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